Red-emitting nitride-based calcium-stabilized phosphors

ABSTRACT

Red-emitting phosphors may comprise a nitride-based composition represented by the chemical formula M a Sr b Si c Al d N e Eu f , wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0&lt;a&lt;1.0; 1.5&lt;b&lt;2.5; 4.0≦c≦5.0; 0≦d≦1.0; 7.5&lt;e&lt;8.5; and 0&lt;f&lt;0.1; wherein a+b+f&gt;2+d/v and v is the valence of M. Furthermore, nitride-based red-emitting phosphor compositions may be represented by the chemical formula M x M′ 2 Si 5-y Al y N 8 :A, wherein: M is Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and x&gt;0; M′ is at least one of Mg, Ca, Sr, Ba, and Zn; 0≦y≦0.15; and A is at least one of Eu, Ce, Tb, Pr, and Mn; wherein x&gt;y/v and v is the valence of M, and wherein the red-emitting phosphors have the general crystalline structure of M′ 2 Si 5 N 8 :A.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/095,766 filed Dec. 3, 2013, which is a continuation of U.S. patentapplication Ser. No. 13/922,231 filed Jun. 19, 2013 (now U.S. Pat. No.8,597,545), which is a continuation-in-part of U.S. patent applicationSer. No. 13/871,961 filed Apr. 26, 2013 (now U.S. Pat. No. 8,663,502),and claims the benefit of U.S. Provisional Patent Application Ser. No.61/673,191 filed Jul. 18, 2012. The disclosures of the aforementionedapplications are all incorporated by reference in their entirety herein.

FIELD OF THE INVENTION

Embodiments of the present invention are directed to red-emittingnitride-based phosphor compositions.

BACKGROUND OF THE INVENTION

Many of the red-emitting phosphors are derived from silicon nitride(Si₃N₄). The structure of silicon nitride comprises layers of Si and Nbonded in a framework of slightly distorted SiN₄ tetrahedra. The SiN₄tetrahedra are joined by a sharing of nitrogen corners such that eachnitrogen is common to three tetrahedra. See, for example, S. Hampshirein “Silicon nitride ceramics—review of structure, processing, andproperties,” Journal of Achievements in Materials and ManufacturingEngineering, Volume 24, Issue 1, September (2007), pp. 43-50.Compositions of red-emitting phosphors based on silicon nitride ofteninvolve substitution of the Si at the center of the SiN₄ tetrahedra byelements such as Al; this is done primarily to modify the opticalproperties of the phosphors, such as the intensity of the emission, andthe peak emission wavelength.

There is a consequence of the aluminum substitution, however, which isthat since Si⁴⁺ is being replaced by Al³⁺, the substituted compounddevelops a missing positive charge. There are essentially two wayscommonly employed to achieve charge balance: in one scheme, an Al³⁺ forSi⁴⁺ substitution is accompanied by a substitution of O²⁻ for N³⁻, suchthat the missing positive charge is counter-balanced with a missingnegative charge. This leads to a network of tetrahedra that have eitherAl³⁺ or Si⁴⁺ as the cations at the centers of the tetrahedra, and astructure whereby either an O²⁻ or an N³⁻ anion is at the corners of thetetrahedra. Since it is not known precisely which tetrahedra have whichsubstitutions, the nomenclature used to describe this situation is(Al,Si)₃—(N,O)₄. Clearly, for charge balance there is one O for Nsubstitution for each Al for Si substitution.

Furthermore, these substitutional mechanisms for charge balance—O forN—may be employed in conjunction with an interstitial insertion of acation. In other words, the modifying cation is inserted between atomspreexisting on crystal lattice sites, into “naturally occurring” holes,interstices, or channels. This mechanism does not require an altering ofthe anionic structure (in other words, a substitution of O for N), butthis is not to say that an O for N substitution may not simultaneouslyoccur. Substitutional mechanisms for charge balance may occur inconjunction with an interstitial insertion of a modifier cation.

The use of modifying cations in nitride phosphors of Sr-containingα-SiAlON has been discussed by K. Shioi et al. in “Synthesis, crystalstructure, and photoluminescence of Sr-α-SiAlON:Eu²⁺ ,” J. Am. CeramSoc., 93 [2] 465-469 (2010). Shioi et al. give the formula for theoverall composition of this class of phosphors:M_(m/v)Si_(12-m-n)Al_(m+n)O_(n)N_(16-n):Eu²⁺, where M is a “modifyingcation” such as Li, Mg, Ca, Y, and rare earths (excluding La, Ce, Pr,and Eu), and v is the valence of the M cation. As taught by Shioi etal., the crystal structure of an α-SiAlON is derived from the compoundα-Si₃N₄. To generate an α-SiAlON from α-Si₃N₄, a partial replacement ofSi⁴⁺ ions by Al³⁺ ions takes place, and to compensate for the chargeimbalance created by Al³⁺ substituting for Si⁴⁺, some O substitutes Nand some positive charges are added by trapping the M cations into theinterstices within the network of (Si,Al)—(O,N)₄ tetrahedra.

Europium doped alkaline earth metal silicon nitride phosphor with thegeneral formula M₂Si₅N₈: Eu, where M is Ca, Sr, or Ba, have been widelystudied, see for example the PhD thesis by JWH van Krevel at theTechnical University Eindhoven, January 2000, and H. A. Hoppe, et al.,J. Phys. Chem. Solids. 2000, 61:2001-2006. In this family of phosphors,pure Sr₂Si₅N₈:Eu has high quantum efficiency and emits at a peakwavelength of about 620 nm. However, this red nitride phosphor has poorstability when used as a coating on an LED operated at a temperature inthe range from 60° C. to 120° C. and an ambient relative humidity in therange from 40% to 90%.

Various research groups have experimented with oxygen-containing M₂Si₅N₈based phosphor materials, which may also contain other metals. Forexample, see U.S. Pat. Nos. 7,671,529 and 6,956,247, and U.S. publishedapplications 2010/0288972, 2008/0081011, and 2008/0001126. However,these oxygen containing phosphor materials are known to exhibit poorstability under the combined conditions of high temperature and highrelative humidity (RH)—for example 85° C. and 85% RH.

The forms of charge compensation reported in the art are not believed torender the phosphor more impervious to thermal/humidity aging, nor dothey appear to accomplish the beneficial result of increasing the peakemission wavelength with little or substantially no alteration ofphotoemission intensity.

There is a need for silicon nitride-based phosphors and M₂Si₅N₈-basedphosphors with peak emission wavelengths over a wider range in the redand also other colors, and with enhanced physical properties of thephosphor, such as temperature and humidity stability.

SUMMARY OF THE INVENTION

Embodiments of the present invention may provide {Mg, Ca, Sr, Ba, Y, Li,Na, K, and/or Zn}-stabilized, particularly Ca-stabilized, nitride-basedphosphors with chemical composition based on M₂Si₅N₈ with and withoutcolumn IIIB elements, particularly Al, substituting for Si. Thestabilizing cations may be (1) incorporated into the phosphor crystalstructure for charge balance for column IIIB element substitution, whenused to substitute for Si, and (2) incorporated into the phosphor inexcess of any need for charge balancing the substitution of Si by acolumn IIIB element. These phosphor materials may be configured toextend the peak emission wavelength to longer wavelengths in the red,and to enhance physical properties of the phosphor—notably, significantimprovement of the temperature and humidity stability.

Some embodiments of the present invention are directed to a red-emittingphosphor which may comprise a nitride-based composition represented bythe chemical formula M_(x)M′₂Si_(5-y)Al_(y)N₈:A, wherein: M is at leastone of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, where v is the valence of M,and x>0; M′ is at least one of Mg, Ca, Sr, Ba, and Zn; y satisfies0≦y≦1.0; and activator A is at least one of Eu, Ce, Tb, Pr, Sin and Mn,wherein x>y/v. Furthermore, the red-emitting phosphor may have thegeneral crystalline structure of M′₂Si₅N₈:A. Yet furthermore, Al maysubstitute for Si within the general crystalline structure and M may belocated within the general crystalline structure substantially atinterstitial sites. Furthermore, the red-emitting phosphor may compriseat least one of F, Cl, Br and O. Yet furthermore, M may be Ca, y=0 and0.1≦x≦0.4. Furthermore, M may be Ca, 0.1≦y≦0.15 and 0.1≦x≦0.4.

Some embodiments of the present invention are directed to a red-emittingphosphor which may comprise a nitride-based composition represented bythe chemical formula M_(a)Sr_(b)Si_(c)Al_(d)N_(e)Eu_(f), wherein: M isat least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0;1.5<b<2.5; 4.0≦c≦5.0; 0≦d≦1.0; 7.5<e<8.5; and 0<f<0.1; whereina+b+f>2+d/v and v is the valence of M. Furthermore, the red-emittingphosphor may comprise at least one of F, Cl, Br and O. Yet furthermore,M may be Ca, d=0 and 0.1≦a≦0.4. Furthermore, M may be Ca, 0.1≦d≦0.15 and0.1≦a≦0.4.

The addition of interstitial Ca to an aluminum substituted M′₂Si₅N₈red-emitting phosphor, beyond any need for charge balancing for thesubstitution of Si by Al, has the unexpected benefit that the stabilityof the phosphor is enhanced under conditions of aging at elevatedtemperature and humidity. In some embodiments, the phosphor may becompositionally configured such that after 800 hours of aging at 85° C.and 85% relative humidity the drop in photoluminescent intensity is nogreater than about 15%, in embodiments no greater than about 10%, andthe deviation in chromaticity coordinates CIE Δx and CIE Δy is less thanor equal to about 0.015 for each coordinate, in embodiments less than orequal to about 0.010 for each coordinate, and in further embodimentsless than or equal to about 0.005 for each coordinate.

Furthermore, the addition of Ca to a M′₂Si₅N₈ red-emitting phosphor hasthe unexpected benefit that the stability of the phosphor is enhancedunder conditions of aging at elevated temperature and humidity. In someembodiments, the phosphor may be compositionally configured such thatafter 500 hours of aging at 85° C. and 85% humidity the drop inphotoluminescent intensity is no greater than about 50%, in embodimentsno greater than about 35%, and the deviation in chromaticity coordinatesCIE Δx and CIE Δy is less than or equal to about 0.065 for eachcoordinate, and in embodiments less than or equal to about 0.045 foreach coordinate.

According to the present embodiments, the phosphor, under blueexcitation, may be configured to emit light having a peak emissionwavelength greater than about 620 nm, in embodiments greater than 623nm, and in further embodiments greater than about 626 nm, where blue maybe defined as light having a wavelength ranging from about 420 nm toabout 470 nm. The present phosphors may also be excited by radiationhaving shorter wavelengths; e.g., from about 200 nm to about 420 nm, butwhen the excitation radiation is in the x-ray or UV, a separateblue-emitting phosphor is provided to contribute a blue component to thedesired white light for a white light source. Furthermore, the presentphosphors may also be excited by radiation having longer wavelengths,wherein the wavelength ranges from about 200 nm to about 550 nm. Acommon blue excitation source is an InGaN LED, or GaN LED, emitting witha peak at about 465 nm.

Embodiments of the present invention also include white light emittingdevice comprising a solid state excitation source and any of thered-emitting phosphors described herein. It may also include ayellow-emitting phosphor and/or a green-emitting phosphor with a peakemission wavelength in the range from about 500 nm to about 580 nm. Anexemplary red-emitting phosphor according to embodiments of the presentinvention is Eu_(0.05)Ca_(0.1)Sr_(1.95)Si_(4.88)Al_(0.12)N₈.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other aspects and features of the present invention willbecome apparent to those ordinarily skilled in the art upon review ofthe following description of specific embodiments of the invention inconjunction with the accompanying figures, wherein:

FIG. 1 shows emission spectra of the red-emitting nitride-basedcalcium-stabilized phosphors Samples 2 through 5, according to someembodiments of the present invention, and Sample 1 is a prior artred-emitting nitride-based 2-5-8 phosphor shown for comparison;

FIG. 2 shows emission spectra of the red-emitting nitride-basedcalcium-stabilized phosphors Samples 6 through 8, according to someembodiments of the present invention, and Sample 1 is shown forcomparison;

FIG. 3 shows emission spectra of the red-emitting nitride-basedcalcium-stabilized phosphors Samples 9 through 12, according to someembodiments of the present invention;

FIG. 4 shows emission spectra of the red-emitting nitride-basedcalcium-stabilized phosphors Samples 13 through 15, according to someembodiments of the present invention;

FIGS. 5A-5D show trends with phosphor calcium content of the peakemission wavelength, peak photoluminescence intensity (PL) and CIE x andy chromaticity coordinates, for red-emitting nitride-basedcalcium-stabilized phosphors Samples 2 through 5 (no aluminum) and 9through 12 (aluminum containing), according to some embodiments of thepresent invention;

FIGS. 6A-6D show trends with phosphor calcium content of the peakemission wavelength, peak photoluminescence intensity (PL) and CIE x andy chromaticity coordinates, for red-emitting nitride-basedcalcium-stabilized phosphors Samples 2 through 4 (additional calcium)and 6 through 8 (substitutional calcium), according to some embodimentsof the present invention;

FIGS. 7A-7C show the results of reliability testing under the conditionsof 85° C. and 85% relative humidity of the red-emitting nitride-basedcalcium-stabilized phosphors Samples 2 through 4, where FIG. 7A is thechange in photoluminescent intensity (brightness) with time, FIG. 7B isthe change in CIE x chromaticity coordinate with time, and FIG. 7C isthe change in CIE y chromaticity coordinate with time, according to someembodiments of the present invention;

FIGS. 8A-8C show the results of reliability testing under the conditionsof 85° C. and 85% relative humidity of the red-emitting nitride-basedcalcium-stabilized phosphors Samples 3 (additional calcium) and 7(substitutional calcium), where FIG. 8A is the change inphotoluminescent intensity (brightness) with time, FIG. 8B is the changein CIE x chromaticity coordinate with time, and FIG. 8C is the change inCIE y chromaticity coordinate with time, according to some embodimentsof the present invention, and reliability data for prior artred-emitting nitride-based 2-5-8 phosphor Sample 1 is shown forcomparison;

FIGS. 9A-9C show the results of reliability testing under the conditionsof 85° C. and 85% relative humidity of the red-emitting nitride-basedcalcium-stabilized phosphors Samples 3 (no aluminum) and 10 (aluminumcontaining), where FIG. 9A is the change in photoluminescent intensity(brightness) with time, FIG. 9B is the change in CIE x chromaticitycoordinate with time, and FIG. 9C is the change in CIE y chromaticitycoordinate with time, according to some embodiments of the presentinvention, and reliability data for prior art red-emitting nitride-based2-5-8 phosphor Sample 1 is shown for comparison;

FIGS. 10A-10C show the results of reliability testing under theconditions of 85° C. and 85% relative humidity of the red-emittingnitride-based calcium-stabilized phosphors Samples 13 through 15, whereFIG. 10A is the change in photoluminescent intensity (brightness) withtime, FIG. 10B is the change in CIE x chromaticity coordinate with time,and FIG. 10C is the change in CIE y chromaticity coordinate with time,according to some embodiments of the present invention;

FIG. 11 shows x-ray diffraction (XRD) patterns of the red-emittingnitride-based calcium-stabilized phosphor Samples 2 through 5, accordingto some embodiments of the present invention, the XRD pattern for Sample1 is shown for comparison;

FIG. 12 shows x-ray diffraction patterns of the red-emittingnitride-based calcium-stabilized phosphor Samples 6 through 8, accordingto some embodiments of the present invention, the XRD pattern for Sample1 is shown for comparison;

FIG. 13 shows x-ray diffraction patterns of the red-emittingnitride-based calcium-stabilized phosphors Samples 9 through 12,according to some embodiments of the present invention, the XRD patternfor Sample 1 is shown for comparison;

FIG. 14 shows x-ray diffraction patterns of the red-emittingnitride-based calcium-stabilized phosphors Samples 13 through 15,according to some embodiments of the present invention, the XRD patternfor Sample 1 is shown for comparison;

FIGS. 15-17 show SEM micrographs of red-emitting nitride-basedcalcium-stabilized phosphors Sample 3 (FIG. 16) (additional calcium) andSample 7 (FIG. 17) (substitutional calcium), according to someembodiments of the present invention, and prior art red-emittingnitride-based 2-5-8 phosphor Sample 1 (FIG. 15) is shown for comparison;

FIG. 18 shows a light emitting device, according to some embodiments ofthe present invention;

FIGS. 19A & 19B show a solid-state light emitting device, according tosome embodiments of the present invention; and

FIG. 20 shows the emission spectrum from a white LED (3000K) comprisinga blue InGaN LED, a red phosphor having the composition of Sample 14,and a yellow/green phosphor, according to some embodiments of thepresent invention.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention will now be described in detailwith reference to the drawings, which are provided as illustrativeexamples of the invention so as to enable those skilled in the art topractice the invention. Notably, the figures and examples below are notmeant to limit the scope of the present invention to a singleembodiment, but other embodiments are possible by way of interchange ofsome or all of the described or illustrated elements. Moreover, wherecertain elements of the present invention can be partially or fullyimplemented using known components, only those portions of such knowncomponents that are necessary for an understanding of the presentinvention will be described, and detailed descriptions of other portionsof such known components will be omitted so as not to obscure theinvention. In the present specification, an embodiment showing asingular component should not be considered limiting; rather, theinvention is intended to encompass other embodiments including aplurality of the same component, and vice-versa, unless explicitlystated otherwise herein. Moreover, applicants do not intend for any termin the specification or claims to be ascribed an uncommon or specialmeaning unless explicitly set forth as such. Further, the presentinvention encompasses present and future known equivalents to the knowncomponents referred to herein by way of illustration.

Some embodiments of the present invention are directed to a red-emittingphosphor which may comprise a nitride-based composition represented bythe chemical formula M_(x)M′₂Si_(5-y)Al_(y)N₈:A, wherein: M is at leastone of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and x>0; M′ is at least oneof Mg, Ca, Sr, Ba, Y, Li and Zn; 0≦y≦1.0; and A is at least one of Eu,Ce, Tb, Pr, Sin and Mn; wherein x>y/v and v is the valence of M—thelatter reflecting the presence of an excess of M for stabilization ofthe phosphor and a larger amount of M than needed for charge balance ofany Al substituting for Si. Furthermore, the red-emitting phosphor maycomprise at least one of F, Cl, Br and O. Yet furthermore, thered-emitting phosphor may have the general crystalline structure ofM′₂Si₅N₈:A; although embodiments of the red-emitting phosphor may existwith other crystalline structures. Furthermore, Al may substitute for Siwithin the general crystalline structure and M may be located within thegeneral crystalline structure substantially at interstitial sites.

According to some further embodiments of the present invention,nitride-based calcium-stabilized phosphors may have a composition givenby the formula Ca_(x)Sr₂Si_(5-y)Al_(y)N₈ where x>0 and 0≦y≦1, whereinthe Ca is present in an amount greater than is required to chargebalance the substitution of Si by Al, in other words where 2 x>y, andwherein the phosphors exhibit good stability under heat and humidity, asspecified herein.

According to further embodiments of the present invention, ared-emitting phosphor may comprise a nitride-based compositionrepresented by the chemical formula M_(a)Sr_(b)Si_(c)Al_(d)N_(e)Eu_(f),wherein: M is at least one of Mg, Ca, Sr, Ba, Y Li, Na, K and Zn, and0<a<1.0; 1.5<b<2.5; 4.0≦c≦5.0; 0≦d≦1.0; 7.5<e<8.5; and 0<f<0.1; whereina+b+f>2+d/v and v is the valence of M—the latter reflecting the presenceof an excess of M for stabilization of the phosphor and a larger amountof M than needed for charge balance of any Al substituting for Si.Furthermore, the red-emitting phosphor may comprise at least one of F,Cl, Br and O. Yet furthermore, M may be Ca, d=0 and 0.1≦a≦0.4, and insome embodiments M may be Ca, d=0 and 0.15≦a≦0.25. Furthermore, M may beCa, 0.1≦d≦0.15 and 0.1≦a≦0.4, and in some embodiments M may be Ca,0.1≦d≦0.15 and 0.15≦a≦0.25.

Some embodiments of the present invention are directed to anitride-based phosphor composition represented by the general formulaM_(x)M′₂A_(5-y)D_(y)E₈:A, where M is a modifier cation. Advantages ofthe modification to the 2-5-8 phosphor include an increase in peakemission wavelength towards the deep red end of the spectrum, and anenhanced stability in elevated thermal and humidity conditions.

M is at least one of a 1+ cation, a 2+ cation, and a 3+ cation, and M′is at least one of Mg, Ca, Sr, Ba, and Zn, used either individually orin combinations. A is at least one of C, Si and Ge, used eitherindividually or in combinations. The element D replaces the A componentsubstitutionally, where D is selected from the group consisting ofcolumn IIIB elements of the periodic table of elements. (The labeling ofthe columns of the periodic table in this disclosure follow the oldIUPAC (International Union of Pure and Applied Chemistry) system. Seehttp://en.wikipedia.org/wiki/Group_(periodic_table), last viewed Jan.15, 2013.) In one embodiment, D is at least one of B, Al, and Ga, usedeither individually or in combinations. E in the general formula of thepresent phosphor is at least one of a 3− anion, a 2− anion, and a 1−anion. Specifically, E may be at least one of O²⁻, N³⁻, F¹⁻, Cl¹⁻, Br⁻,and I⁻, used either individually or in combinations. The activator, A,is at least one of Eu, Ce, Tb, Pr, Sm and Mn. Herein “A” represents aphosphor activator and the notation “:A” represents doping by a rareearth and/or Mn which is generally substitutional, but may also includedoping at grain boundaries, on particle surfaces and in interstitialsites within the crystalline structure of the phosphor material. Theparameter y is given by 0≦y≦1.0 and the value of the parameter x may bedefined as being greater than the value of y divided by the valence ofM, such that M is present in an amount greater than required for chargebalance of any substitution of A by D.

The modifier cation M is added to the phosphor in an amount which isgreater than is required to charge compensate for the substitution of Dfor A. Specifically, M may be at least one of Li¹⁺, Na¹⁺, K¹⁺, Sc³⁺,Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, B³⁺ and Y³⁺, used either individually orin combinations. M is an extra cation, utilized in addition to thestoichiometric amount of the divalent metal M′ in the formula M′₂Si₅N₈,and as such, it is expected that this modifier cation might be insertedinto the phosphor substantially interstitially, although M may occupyother positions within the host lattice.

Interstitial sites are cavities, holes, or channels that exist in thecrystalline lattice by virtue of the manner in which the host'sconstituent atoms are arranged (packed, or stacked). Dopant atoms thatoccupy the interstices of a crystal are to be distinguished from suchatoms introduced substitutionally; in this latter mechanism, the dopantatoms replace host atoms residing on crystal lattice sites. Support forthe proposed interstitial placement of modifier cations within thestructure of the phosphor material is found in the literature forceramic materials with an α-silicon nitride crystal structure. Forexample, see Hampshire et al. “α′-Sialon ceramics”, Nature 274, 880(1978) and Huang et al. “Formation of α-Si₃N₄ Solid Solutions in theSystem Si₃N₄—AlN—Y₂O₃” J. Amer. Ceram. Soc. 66 (6), C-96 (1983). Thesearticles state that it is known that the α-silicon nitride unit cellcontains two interstitial sites large enough to accommodate other atomsor ions. Furthermore, the α′-sialon structure is derived from theα-silicon nitride structure by partial replacement of Si with Al, andvalency compensation is effected by cations—such as Li, Ca, Mg andY—occupying the interstices of the (Si, Al)—N network, and also byoxygen replacing nitrogen when an oxide is used. (The α′-sialonstructure is represented by M_(x)(Si, Al)₁₂(O, N)₁₆, where x is notgreater than 2.) Yet furthermore, it is accepted that the a r-sialonstructure requires the equivalent of at least half a cationic valency ineach of the two interstices within the unit cell to stabilize thestructure.

Generally, the crystalline structures of the 2-5-8 nitride-basedcompounds as described herein may have a space group selected fromPmn2₁, Cc, derivatives thereof, or mixtures thereof. In some examples,the space group is Pmn2₁. Furthermore, it should be noted that inmaterials science theory the vacancy density of a pure crystallinematerial may be on the order of a hundred parts per million of theexisting lattice sites depending on the thermal equilibrium conditionsof the crystal. As such, a small percentage of the modifier ions, M, mayend up in vacant metal ion sites, rather than the interstitial sites—themodifier ions filling the vacancies before the interstitial sites.

Furthermore, the modifier ions may also be involved in charge balancingto compensate for the presence of anions of elements such as F, Cl, Brand O within the phosphor, either substituting for N within the M′₂Si₅N₈crystal lattice, or filling interstitial positions within the crystallattice. These anions may either be present in the phosphor materialintentionally, or as contaminants. Contaminants, such as oxygen, may befrom environmental sources. According to some embodiments, the phosphormay have halide and/or oxygen intentionally introduced in a range from 0to about 6 mole percent. Halide may be added by using one or morestarting materials comprising a halide, for example: EuCl₃, EuF₃, EuBr₃,NH₄F, etc. Oxygen may be added by using one or more starting materialscomprising an oxide, for example: Eu₂O₃, SiO₂, etc. Furthermore, themethods for controllably incorporating oxygen in to the phosphormaterial that are described in U.S. patent application Ser. No.13/871,961, incorporated herein by reference in its entirety, may beused for incorporation of oxygen into the phosphors of the presentinvention.

Next the disclosure will present phosphors based on the present modifiercation-stabilized M_(x)M′₂A_(5-y)D_(y)E₈:A embodiments, giving theiradvantages and properties, and how these phosphors differ from the priorart. Specific examples will be given, including a phosphor wherein thecolumn IIIB element substituting for Si⁴⁺ is Al³⁺, and wherein themodifying cation is Ca²⁺, and other examples in which y=0. Acceleratedaging results will be discussed which show the superior thermal andchemical stability of the phosphors of the present invention over otherprior art 2-5-8 based phosphors. Finally, SEM micrographs will show thechange in morphology of the phosphor crystals as the amount of Ca isincreased beyond the amount used to charge balance the substitution ofSi by Al.

Discussion of the Present Phosphors Based on Ca_(x)Sr₂Si_(5-y)Al_(y)N₈:A

Fifteen different phosphor samples were prepared as described in moredetail below with reference to Tables 1A, 1B, 2A, 2B, 3A, 3B, 4A and 4B.PL spectra, CIE coordinates, XRD and SEM data were collected forsamples, as discussed in more detail below.

Sample 1 is a well-known 2-5-8 red-emitting nitride phosphor used hereinas a control; it has the composition Sr_(1.95)Si₅N₈Eu_(0.05). Samples 2through 5 are based on the composition of Sample 1, but with increasingamounts of calcium added as modifier cations; in these samples themodifier cations do not have a charge compensation role to play, for Sisubstitution at least. These samples have a composition represented bythe formula Ca_(x)Sr_(1.95)Si₅N₈Eu_(0.05).

Samples 6 through 8 are based on the composition of Sample 1, but withcalcium substituting for strontium in increasing amounts; in thesesamples the modifier cations do not have a charge compensation role toplay. These samples have a composition represented by the formulaCa_(x)Sr_(1.95-x)Si₅N₈Eu_(0.05). These Samples are compared with Samples2 through 4 which have the same amount of calcium added, but in Samples2 through 4 the calcium does not substitute for strontium—it is inaddition to the strontium and is expected to be present in the phosphorcrystal in interstitial lattice positions.

Samples 9 through 12 are based on the composition of Sample 1, but with(1) some aluminum substituted for silicon, and (2) with increasingamounts of calcium added as modifier cations, where the calcium is BOTHplaying the role of charge compensation for the substitution of aluminumfor silicon, and is present in amounts beyond what is needed for chargecompensation and may result in improved phosphor stability underconditions of heat and humidity. These samples have a compositionrepresented by the formula Ca_(x)Sr_(1.95)Si_(4.9) Al_(0.1)N₈Eu_(0.05).

Samples 13 through 15 are similar to Samples 9 through 12, except forthe amount of aluminum being slightly greater in Samples 13 through 15.These samples have a composition represented by the formulaCa_(x)Sr_(1.95)Si_(4.88)Al_(0.12)N₈Eu_(0.05). Furthermore, Sample 13 hasonly enough additional calcium to charge compensate the substitution ofaluminum for silicon, whereas Samples 14 & 15 have amounts of calciumbeyond what is needed for charge compensation.

According to some embodiments, the phosphors, under blue excitation, maybe configured to emit light having a peak emission wavelength greaterthan about 620 nm, in embodiments greater than 623 nm, and in furtherembodiments greater than about 626 nm, where blue may be defined aslight having a wavelength ranging from about 420 nm to about 470 nm. Thepresent phosphors may also be excited by radiation having shorterwavelengths; e.g., from about 200 nm to about 420 nm, but when theexcitation radiation is in the x-ray or UV, a separate blue-emittingphosphor is provided to contribute a blue component to the desired whitelight for a white light source. Furthermore, the present phosphors mayalso be excited by radiation having longer wavelengths, wherein thewavelength ranges from about 200 nm to about 550 nm. A common blueexcitation source is an InGaN LED, or GaN LED, emitting with a peak atabout 460 nm.

FIGS. 5A-5D show trends based on the phosphor calcium content of thepeak emission wavelength, peak photoluminescence intensity (PL) and CIEx and y chromaticity coordinates, for red-emitting nitride-basedcalcium-stabilized phosphors Samples 2 through 5 (no aluminum) and 9through 12 (aluminum containing), according to some embodiments of thepresent invention. All of these phosphors have excess calcium, beyondwhat is required for charge balance in the case of thealuminum-containing samples; and all of these phosphors are assumed tohave the calcium present in the crystal structure at interstitial sites.The trends for the no aluminum and the aluminum-containing samples arevery similar, suggesting that the trends may be dominated by theinterstitial calcium content.

FIGS. 6A-6D show trends with phosphor calcium content of the peakemission wavelength, peak photoluminescence intensity (PL) and CIE x andy chromaticity coordinates, for red-emitting nitride-basedcalcium-stabilized phosphors Samples 2 through 4 (additional calcium)and 6 through 8 (substitutional calcium), according to some embodimentsof the present invention. There is an appreciable difference in thetrends between the additional (assumed interstitial) calcium and thesubstitutional calcium, suggesting the location of the calcium withinthe crystal lattice may be significant.

Reliability Testing

Within many territories including the United States, regulatory bodiesset performance criteria for replacement LED lamps. For example the USEnvironmental Protection Agency (EPA) in conjunction with the USDepartment of Energy (DOE) promulgates performance specifications underwhich a lamp may be designated as an “ENERGY STAR®” compliant product,e.g. identifying the power usage requirements, minimum light outputrequirements, luminous intensity distribution requirements, luminousefficacy requirements, life expectancy, etc. The ENERGY STAR® “ProgramRequirements for Integral LED Lamps” requires that for all LED lamps“the change of chromaticity over the minimum lumen maintenance testperiod (6000 hours) shall be within 0.007 on the CIE 1976 (u′,v′)diagram” and depending on lamp type, the lamp must have “70% lumenmaintenance (L70) at 15,000 or 25,000 hours of operation”. The ENERGYSTAR® requirements are for the lamp performance and include allcomponents of the lamp such as the LEDs, phosphor, electronic drivercircuitry, optics and mechanical components. In principal, thedegradation in brightness of a white LED with aging can be due not onlyto the phosphor, but also to the blue LED chip. Additional sources ofdegradation can come from the packaging materials (such as thesubstrate), the bond wires and other components encapsulated withsilicone. In contrast, the factors affecting the change in colorcoordination are dominated primarily by phosphor degradation. In termsof phosphor performance it is believed that in order to comply withENERGY STAR® requirements would require a change in chromaticity (CIEΔx, CIE Δy) of ≦0.01 for each coordinate over 1000 hours for thephosphor under accelerated testing at 85° C. and 85% relative humidity.The accelerated testing is done on phosphor coated 3000K white LEDsprepared as follows: phosphor particles are combined with a binder, suchas epoxy or silicone, and then applied to the LED chip. The coated LEDis placed in an oven at the specified temperature and humidity andoperated continuously for the testing period.

FIGS. 7A-7C, 8A-8C, 9A-9C and 10A-10C show the results of reliabilitytesting under the conditions of 85° C. and 85% relative humidity ofphosphor Samples 2 through 4, Samples 1, 3 and 7, Samples 1, 3 and 10and Samples 13 through 15, respectively. The figures show the change inphotoluminescent intensity (brightness) with time, the change in CIE xchromaticity coordinate with time, and the change in CIE y chromaticitycoordinate with time. The Sr₂Si₅N₈:Eu control sample (Sample 1) showedresults that would typically be unacceptable to the industry—all otherSamples showed different levels of improvement over the control, thebest performance being shown by Samples 10 & 15 which will most likelysatisfy the typical industry heat and humidity stability requirement.

In more detail, FIGS. 7A-7C show an improvement in reliability withincrease in additional calcium content of the no aluminum-contentphosphors. FIGS. 8A-8C compare the control with a substitutional calciumphosphor and an additional calcium phosphor—all phosphors withoutaluminum and where the two calcium-containing phosphors differ incomposition only in that Sample 3 has more strontium than Sample 7,since in Sample 7 the calcium has substituted for strontium; the bestreliability is seen for the phosphor with additional calcium. FIGS.9A-9C compare the control with an additional calcium phosphor withoutaluminum and an additional calcium phosphor with aluminum—the twocalcium-containing phosphors differ in composition only in that Sample10 contains aluminum and Sample 3 does not; the best reliability is seenfor the phosphor containing aluminum. FIGS. 10A-10C show an improvementin reliability for the additional calcium phosphors with increase incalcium content. In summary, the most significant improvement instability over the control (Sample 1), as defined by maintainingintensity and chromaticity, is realized by Ca interstitial chargebalancing and Al substituting for Si, plus excess interstitial Ca(beyond what is required for charge balance of the Al); the beststability results are seen for the higher Ca/Al ratio materials, asexemplified by Samples 10 & 15 (see Tables 3B & 4B). It should be notedthat Samples 10 & 15 are uncoated phosphors, and yet shows excellentstability—stability data is shown for up to 800 hours for Sample 15 andit is expected that after 1000 hours Sample 15 will meet the acceleratedtesting criteria used to establish ENERGY STAR® compliance. Even thoughSamples 10 & 15 show excellent stability without coating, Samples 10 &15 can be coated to provide expected further stability improvement.Similarly, other Samples can be coated to improve stability.

To provide a potential further improvement in performance the particlesof the phosphor with the composition of the Samples of the presentinvention can be coated with one or more coatings of, for example, SiO₂,Al₂O₃ and/or TiO₂, as taught in co-pending patent applications U.S.application Ser. No. 13/671,501 for COATINGS FOR PHOTOLUMINESCENTMATERIALS and U.S. application Ser. No. 13/273,166 for HIGHLY RELIABLEPHOTOLUMINESCENT MATERIALS HAVING A THICK AND UNIFORM TITANIUM DIOXIDECOATING, the content of each of which is incorporated in its entirety byway of reference thereto.

XRD of the Present Phosphor Compositions

FIGS. 11-14 show XRD patterns of red-emitting nitride-based phosphors ofthe present invention; the XRD pattern for sample 1 is shown forcomparison.

Morphology of Phosphor Particles of the Present Phosphor Compositions

FIGS. 15-17 show secondary electron micrographs of as preparedred-emitting nitride-based calcium-stabilized phosphors Sample 3 (FIG.16) (additional calcium) and. Sample 7 (FIG. 17) (substitutionalcalcium), according to some embodiments of the present invention, andprior art red-emitting nitride-based 2-5-8 phosphor Sample 1 (FIG. 15)is shown for comparison. All of FIGS. 15-17 show some particles with ahigher aspect ratio (length to width)—in excess of 3. Furthermore, acomparison of FIGS. 15-17 suggests that the percentage of high aspectratio particles is greater for the control (FIG. 15) than for thesamples of the phosphors of the present invention.

Synthesis of the Present Phosphors

For each of the examples and comparative examples described herein, thestarting materials included at least one of the compounds Si₃N₄, AlN,Ca₃N₂, Sr₃N₂, BN, GaN, SiO₂, Al₂O₃, and EuCl₃.

Samples 1 through 5

To obtain desired compositions of the phosphors exemplified in Samples 1through 5, solid powders were weighed according to the compositionslisted in Table 1A. This mixture of raw materials were then loaded intoa plastic milling bottle together with milling beads, sealed in a glovebox, followed by a ball milling process for about 2 hours. The mixedpowders were then loaded into a molybdenum crucible having an innerdiameter of 30 mm and a height of 30 mm; the loaded crucible was coveredwith a molybdenum lid and placed into a gas sintering furnace equippedwith a graphite heater.

After loading the crucible, the furnace was evacuated to 10⁻² Pa, andthe sample heated to 150° C. under these vacuum conditions. At the 150°C. temperature, a high purity N₂ gas was introduced into the chamber;the temperature of the furnace was then increased to about 1700° C. at asubstantially constant heating rate of 4° C./min. The samples weremaintained at 1700° C. for about 7 hours.

After firing, the power was shut off and the samples allowed to cool inthe furnace. The as-sintered phosphor was ground slightly, ball milledto a certain particle size, followed by a wash, dry and sieve procedure.The final product was tested using an Ocean Optics USB4000 spectrometerfor photoluminescence intensity (PL) and chromaticity (CIE coordinates xand y). The x-ray diffraction (XRD) patterns of the phosphors weremeasured using the K_(α) line of a Cu target. The test results arelisted in Table 1B.

A flux, such as ammonium chloride, may also be used in the fabricationof the phosphors of the present invention.

FIG. 1 is the emission spectra of the phosphors from Samples 1 through5. Powder x-ray diffraction measurements using the K_(α) line of a Cutarget are shown in FIG. 11 for the phosphors of Samples 1 through 5.

TABLE 1A Composition of starting raw materials for Samples 1 through 5Compound EuCl₃ Sr₃N₂ Ca₃N₂ Si₃N₄ AlN Sample 1 5.166 75.62 0 93.52 0Sample 2 2.583 37.81 0.988 46.76 0 Sample 3 2.583 37.81 1.976 46.76 0Sample 4 2.583 37.81 2.964 46.76 0 Sample 5 2.583 37.81 3.952 46.76 0

TABLE 1B Emission Peak wavelength, Intensity and CIE of Samples 1through 5 with Composition Ca_(x)Sr_(1.95)Si₅N₈Eu_(0.05) Test ResultsEmission Ca Peak PL Content, Al Wavelength Intensity CIE CIE Sample xContent (nm) (a.u.) (x) (y) 1 0 0 622.77 1.56 0.6423 0.3573 2 0.1 0624.10 1.62 0.6449 0.3547 3 0.2 0 626.29 1.61 0.6584 0.3511 4 0.3 0628.64 1.60 0.6493 0.3502 5 0.4 0 630.16 1.56 0.6517 0.3477

Samples 6 through 8

To obtain the desired compositions of the phosphors of Samples 6 through8, solid powders were weighed according to the compositions listed inTable 2A. The same synthesis procedure as that used for Samples 1through 5 was used. The test results are listed in Table 2B.

The emission spectra of phosphor Samples 6 through 8 are shown in FIG.2. X-ray diffraction measurements using the K_(α) line of a Cu targetwere obtained, and the XRD patterns of Samples 6 through 8 are shown inFIG. 12.

TABLE 2A Composition of starting raw materialsfor Samples 6 through 8Compound EuCl₃ Sr₃N₂ Ca₃N₂ Si₃N₄ AlN Sample 6 2.583 35.87 0.988 46.76 0Sample 7 2.583 33.93 1.976 46.76 0 Sample 8 2.583 31.99 2.964 46.76 0

TABLE 2B Emission Peak wavelength, Intensity and CIE of Samples 6through 8 with Composition Ca_(x)Sr_(1.95-x)Si_(5-y)Al_(y)N₈Eu_(0.05)Test Results Emission Ca Al Peak PL Content, Content, WavelengthIntensity CIE CIE Sample x y (nm) (a.u.) (x) (y) 6 0.1 0 624.54 1.660.6443 0.355 7 0.2 0 627.86 1.57 0.6476 0.352 8 0.3 0 631.08 1.51 0.65000.350

Samples 9 through 12

To obtain the desired compositions of the phosphors of Samples 9 through12, solid powders were weighed according to the compositions listed inTable 3A. The same synthesis procedure as that used for Samples 1through 5 was used. The test results are listed in Table 3B.

FIG. 3 is the emission spectra of the phosphors from Samples 9 through12. X-ray diffraction measurements using the K_(α) line of a Cu targetwere obtained, and the XRD patterns of Samples 9-12 are shown in FIG.13.

TABLE 3A Composition of starting raw materials for Samples 9 through 12Compound EuCl₃ Sr₃N₂ Ca₃N₂ Si₃N₄ AlN Sample 9  2.583 37.81 0.988 45.830.82 Sample 10 2.583 37.81 1.976 45.83 0.82 Sample 11 2.583 37.81 2.96445.83 0.82 Sample 12 2.583 37.81 3.952 45.83 0.82

TABLE 3B Emission Peak wavelength, Intensity and CIE of Samples 9through 12 with Composition Ca_(x)Sr_(1.95)Si_(4.9)Al_(0.1)N₈Eu_(0.05)Test Results Emission Ca Peak PL Content, Al Wavelength Intensity CIECIE Sample x Content (nm) (a.u.) (x) (y)  9 0.1 0.1 626.50 1.56 0.64420.3554 10 0.2 0.1 628.42 1.52 0.6470 0.3526 11 0.3 0.1 630.75 1.460.6476 0.3520 12 0.4 0.1 632.71 1.41 0.6504 0.3492

Samples 13 through 15

To obtain the desired compositions of the phosphors of Samples 13through 15, solid powders were weighed according to the compositionslisted in Table 4A. The same synthesis procedure as that used forSamples 1 through 5 was used. The test results are listed in Table 4B.

FIG. 4 is the emission spectra of the phosphors from Samples 13 through15. X-ray diffraction measurements using the K_(α) line of a Cu targetwere obtained, and the XRD patterns of Samples 13-15 are shown in FIG.14.

TABLE 4A Composition of starting raw materials for Samples 13 through 15Compound EuCl₃ Sr₃N₂ Ca₃N₂ Si₃N₄ AlN Sample 13 5.166 75.622 1.186 91.281.968 Sample 14 5.166 75.622 1.976 91.28 1.968 Sample 15 5.166 75.6223.592 91.28 1.968

TABLE 4B Emission Peak wavelength, Intensity and CIE of Samples 13through 15 with Composition Ca_(x)Sr_(1.95)Si_(4.88)Al_(0.12)N₈Eu_(0.05)Test Results Emission Ca Peak Content, Al Wavelength Intensity CIE CIESample x Content (nm) (a.u.) (x) (y) 13 0.06 0.12 625 1.66 0.6450 0.3540(charge balanced) 14 0.1 0.12 626 1.59 0.6459 0.3538 (Ca excess) 15 0.20.12 629 1.52 0.6478 0.3518 (Ca excess)

Those of ordinary skill in the art will appreciate that compositionsbeyond those specifically described above may be made using the methodsdescribed above with some different choices of elements. For example,phosphor compositions may be made which are represented by the chemicalformula M_(a)Sr_(b)Si_(c)Al_(d)N_(e)Eu_(f), wherein: M is at least oneof Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5;4.0≦c≦5.0; 0≦d≦1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v isthe valence of M. Furthermore, phosphor compositions may be made whichare represented by the chemical formula M_(x)M″₂Si_(5-y)Al_(y)N₈:A,wherein: M is Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and x>0; M′ is atleast one of Mg, Ca, Sr, Ba, and Zn; 0≦y≦0.15; and A is at least one ofEu, Ce, Tb, Pr, and Mn; wherein x>y/v and v is the valence of M, andwherein the phosphors have the general crystalline structure ofM′₂Si₅N₈:A.

FIG. 18 illustrates a light emitting device, according to someembodiments. The device 10 can comprise a blue light emitting, withinthe range of 450 nm to 470 nm, GaN (gallium nitride) LED chip 12, forexample, housed within a package. The package, which can for examplecomprise a low temperature co-fired ceramic (LTCC) or high temperaturepolymer, comprises upper and lower body parts 16, 18. The upper bodypart 16 defines a recess 20, often circular in shape, which isconfigured to receive the LED chips 12. The package further compriseselectrical connectors 22 and 24 that also define corresponding electrodecontact pads 26 and 28 on the floor of the recess 20. Using adhesive orsolder, the LED chip 12 can be mounted to a thermally conductive padlocated on the floor of the recess 20. The LED chip's electrode pads areelectrically connected to corresponding electrode contact pads 26 and 28on the floor of the package using bond wires 30 and 32 and the recess 20is completely filled with a transparent polymer material 34, typically asilicone, which is loaded with a mixture of a yellow and/or greenphosphor and a red phosphor material of the present invention such thatthe exposed surfaces of the LED chip 12 are covered by thephosphor/polymer material mixture. To enhance the emission brightness ofthe device the walls of the recess are inclined and have a lightreflective surface.

FIGS. 19A and 19B illustrate a solid-state light emitting device,according to some embodiments. The device 100 is configured to generatewarm white light with a CCT (Correlated Color Temperature) ofapproximately 3000K and a luminous flux of approximately 1000 lumens andcan be used as a part of a downlight or other lighting fixture. Thedevice 100 comprises a hollow cylindrical body 102 composed of acircular disc-shaped base 104, a hollow cylindrical wall portion 106 anda detachable annular top 108. To aid in the dissipation of heat, thebase 104 is preferably fabricated from aluminum, an alloy of aluminum orany material with a high thermal conductivity. The base 104 can beattached to the wall portion 106 by screws or bolts or by otherfasteners or by means of an adhesive.

The device 100 further comprises a plurality (four in the exampleillustrated) of blue light emitting LEDs 112 (blue LEDs) that aremounted in thermal communication with a circular-shaped MCPCB (metalcore printed circuit board) 114. The blue LEDs 112 can comprise aceramic packaged array of twelve 0.4 W GaN-based (gallium nitride-based)blue LED chips that are configured as a rectangular array 3 rows by 4columns.

To maximize the emission of light, the device 100 can further compriselight reflective surfaces 116 and 118 that respectively cover the faceof the MCPCB 114 and the inner curved surface of the top 108. The device100 further comprises a photoluminescent wavelength conversion component120 that is operable to absorb a proportion of the blue light generatedby the LEDs 112 and convert it to light of a different wavelength by aprocess of photoluminescence. The emission product of the device 100comprises the combined light generated by the LEDs 112 and thephotoluminescent wavelength conversion component 120. The wavelengthconversion component is positioned remotely to the LEDs 112 and isspatially separated from the LEDs. In this patent specification“remotely” and “remote” means in a spaced or separated relationship. Thewavelength conversion component 120 is configured to completely coverthe housing opening such that all light emitted by the lamp passesthrough the component 120. As shown the wavelength conversion component120 can be detachably mounted to the top of the wall portion 106 usingthe top 108 enabling the component and emission color of the lamp to bereadily changed.

FIG. 20 shows the emission spectrum from a white light emitting device,such as described above with reference to FIGS. 18, 19A & 19B,comprising a blue-emitting InGaN LED, a red phosphor having thecomposition of Sample 14, and one or more yellow/green phosphors withpeak emission within the range of 500 nm to 580 nm, such as a phosphordescribed in U.S. patent application Ser. No. 13/181,226 and U.S. patentapplication Ser. No. 13/415,623, both incorporated by reference hereinin their entirety. In further embodiments, the yellow/green phosphor maybe a silicate. Yet furthermore, the white LED may further compriseanother phosphor as may be needed to achieve a desired emissionspectrum, for example an orange aluminate.

Although the present invention has been particularly described withreference to certain embodiments thereof, it should be readily apparentto those of ordinary skill in the art that changes and modifications inthe form and details may be made without departing from the spirit andscope of the invention.

What is claimed is:
 1. A red-emitting phosphor comprising anitride-based composition represented by the chemical formulaM_(a)Sr_(b)Si_(c)Al_(d)N_(e)Eu_(f), wherein: M is at least one of Mg,Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0≦c≦5.0;0≦d≦1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is thevalence of M.
 2. The red-emitting phosphor of claim 1, furthercomprising at least one of F, Cl, Br and O.
 3. The red-emitting phosphorof claim 1, wherein M is Ca, d=0 and 0.1≦a≦0.4.
 4. The red-emittingphosphor of claim 3, wherein said red-emitting phosphor is selected fromthe group consisting of: Eu_(0.05)Ca_(0.1)Sr_(1.95)Si₅N₈;Eu_(0.05)Ca_(0.2)Sr_(1.95)Si₅N₈; Eu_(0.05)Ca_(0.3)Sr_(1.95)Si₅N₈; andEu_(0.05)Ca_(0.4)Sr_(1.95)Si₅N₈.
 5. The red-emitting phosphor of claim3, wherein said red-emitting phosphor absorbs radiation at a wavelengthranging from about 200 nm to about 550 nm and emits light with aphotoluminescence peak emission wavelength greater than 620.0 nm.
 6. Thered-emitting phosphor of claim 1, wherein M is Ca, 0.1≦d≦0.15 and0.1≦a≦0.4.
 7. The red-emitting phosphor of claim 6, wherein saidred-emitting phosphor is selected from the group consisting of:Eu_(0.05)Ca_(0.1)Sr_(1.95)Si_(4.9)Al_(0.1)N₈;Eu_(0.05)Ca_(0.2)Sr_(1.95)Si_(4.9)Al_(0.1)N₈;Eu_(0.05)Ca_(0.3)Sr_(1.95)Si_(4.9)Al_(0.1)N₈;Eu_(0.05)Ca_(0.4)Sr_(1.95)Si_(4.9)Al_(0.1)N₈;Eu_(0.05)Ca_(0.1)Sr_(1.95)Si_(4.88)Al_(0.12)N₈; andEu_(0.05)Ca_(0.2)Sr_(1.95)Si_(4.88)Al_(0.12)N₈.
 8. The red-emittingphosphor of claim 6, wherein said red-emitting phosphor is configuredsuch that under excitation by a blue LED the reduction inphotoluminescent intensity after 800 hours of aging at about 85° C. andabout 85% humidity is no greater than about 15%.
 9. The red-emittingphosphor of claim 6, wherein said red-emitting phosphor is configuredsuch that the deviation in chromaticity coordinates CIE Δx and CIE Δyafter 800 hours of aging at about 85° C. and about 85% relative humidityis less than or equal to about 0.015 for each coordinate.
 10. Thered-emitting phosphor of claim 9, wherein the deviation in chromaticitycoordinates CIE Δx and CIE Δy is less than or equal to about 0.005 foreach coordinate.
 11. The red-emitting phosphor of claim 6, wherein saidred-emitting phosphor absorbs radiation at a wavelength ranging fromabout 200 nm to about 550 nm and emits light with a photoluminescencepeak emission wavelength greater than 620.0 μm.
 12. The red-emittingphosphor of claim 1, wherein said red-emitting phosphor has the generalcrystalline structure of Sr₂Si₅N₈: Eu with M and Al incorporatedtherein.
 13. The red-emitting phosphor of claim 12, wherein Alsubstitutes for Si within said general crystalline structure and M islocated within said general crystalline structure substantially atinterstitial sites.
 14. The red-emitting phosphor of claim 1, whereinsaid red-emitting phosphor consists of Ca, Sr, Si, Al, N, Eu and atleast one of F, Cl, Br and O.
 15. A red-emitting phosphor comprising anitride-based composition represented by the chemical formulaM_(x)M′₂Si_(5-y)Al_(y)N₈:A, wherein: M is at least one of Mg, Ca, Sr,Ba, Y and Li, and x>0; M′ is at least one of Mg, Ca, Sr, Ba, Y and Li;0≦y≦1; and A is at least one of Eu, Ce, Tb, Pr, Sm and Mn; wherein x>y/vand v is the valence of M, and wherein said red-emitting phosphor hasthe general crystalline structure of M′₂Si₅N₈:A.
 16. The red-emittingphosphor of claim 15, wherein M is the same as M′.
 17. The red-emittingphosphor of claim 15, wherein said red-emitting phosphor absorbsradiation at a wavelength ranging from about 200 nm to about 550 nm andemits light with a photoluminescence peak emission wavelength greaterthan 620.0 nm.
 18. The red-emitting phosphor of claim 15, wherein saidred-emitting phosphor is configured such that the deviation inchromaticity coordinates CIE Δx and CIE Δy after 800 hours of aging atabout 85° C. and about 85% relative humidity is less than or equal toabout 0.015 for each coordinate.
 19. The red-emitting phosphor of claim18, wherein the deviation in chromaticity coordinates CIE Δx and CIE Δyis less than or equal to about 0.005 for each coordinate.
 20. Thered-emitting phosphor of claim 15, further comprising at least one of F,Cl, Br and O.
 21. The red-emitting phosphor of claim 15, wherein saidred-emitting phosphor consists of Ca, Sr, Si, Al, N, Eu and at least oneof F, Cl, Br and O.
 22. The red-emitting phosphor of claim 15, whereinM′ is Sr.
 23. The red-emitting phosphor of claim 22, wherein M is Ca.24. The red-emitting phosphor of claim 15, wherein RE is Eu.
 25. Thered-emitting phosphor of claim 15, wherein y=0 and 0.1≦x≦0.4.
 26. Thered-emitting phosphor of claim 15, wherein 0.1≦y≦0.15 and 0.1≦x≦0.4. 27.A white light emitting device comprising: a solid state excitationsource with emission wavelength within a range from 200 nm to 480 nm; ared-emitting phosphor according to claim 1, said red-emitting phosphorbeing configured to absorb excitation radiation from said excitationsource and to emit light having a peak emission wavelength in the rangefrom about 620 nm to about 650 nm; and a yellow/green-emitting phosphorhaving a peak emission wavelength in the range from about 500 nm toabout 580 nm.
 28. The white light emitting device of claim 27, whereinsaid red-emitting phosphor is configured to absorb excitation radiationfrom said excitation source and to emit light having a peak emissionwavelength in the range from about 624 nm to about 632 nm.
 29. The whitelight emitting device of claim 27, wherein said red-emitting phosphorhas the formula Eu_(0.05)Ca_(0.1)Sr_(1.95)Si_(4.88)Al_(0.12)N₈.
 30. Thewhite light emitting device of claim 27, wherein said excitation sourcehas an emission wavelength within a range from 450 nm to 470 nm.